This contribution reports the first successful coordination-addition polymerization of N,N-dialkylmethacrylamides and the first example of kinetic resolution of a racemic methacrylamide by chiral metallocene catalysts. The polymerization of methacryloyl-2-methylaziridine (MMAz) by rac-(EBI)Zr+-(THF)[OC((OPr)-Pr-i)=CMe2][MeB(C6F5)(3)](-) (1) is stereospecific and also exhibits a high degree of. control over polymerization. This polymerization follows first-order kinetics in both concentrations of monomer and catalyst, consistent with a monometallic propagation mechanism involving the fast step of intramolecular conjugate addition within the catalyst-monomer coordination complex leading to the eight-membered-ring resting intermediate. Substituents on the highly strained aziridine ring stabilize the aziridine moiety against thermally induced cross-linking through its ring-opening reaction; thus, the polymer derived from methacryloyl-tetramethyleneaziridine (MTMAz) exhibits greatly enhanced resistance toward thermal cross-linking over poly(MMAz), marking 57 and 42 degrees C higher onset cross-linking and maximum cross-linking temperatures, respectively. Enantiomeric catalyst (S,S)-1 demonstrates experimentally and theoretically its ability to kinetically resolve the racemic MMAz monomer with a low stereoselectivity factor s of 1.8. Polymerizability of several methacrylamide monomers has been investigated via a combined experimental and theoretical (DFT) study that examines the degree of conjugation between the vinyl and carbonyl double bonds, relative polymerization reactivity, and relative energy for the formation of amide-enolate intermediates.